A geochemical survey of Belgium and Luxembourg was carried out as part of an international research project entitled 'Regional geochemical mapping of Western Europe towards the year 2000'. The aim of this research was to map regional background geochemical patterns based on pristine or at least pre-industrial overbank samples and to deduce regional information on the degree of environmental pollution of floodplain and present-day river sediments. Over the entire study area (about 33,000 km(2)), 66 overbank sites have been sampled. Catchment areas range between 60 and 600 km(2). At each site an overbank profile has been dug out in the immediate vicinity of the river and described in detail. A first composite sample was taken 5-25 cm below the surface. This sample is supposed to represent deposition over the last centuries. Human interferences in this interval are often inferable based on changed sedimentary characteristics and the presence of anthropogenic particles such as charcoal, slags and brick fragments. ii second composite sample was taken at depth, usually >1.5 m below the surface over an interval of about 20 cm. In most sites, the profile characteristics allowed to assume pre-industrial or even pristine conditions for this lower overbank sample. In some profiles this was confirmed by C-14-dating and/or by the absence of anthropogenic particles. Finally, a present-day stream sediment was sampled on the site to infer the actual pollution status. After drying at 80 degrees C, disaggregation and sieving, the <125 mu m fractions of the three sediment samples were analysed by XRF for major elements and several trace elements. Lower overbank samples generally show a direct link with the geological substrate and allow to assess natural background concentrations. Results from the mapping exercise as well as from the statistical analyses display a clear contrast between the northern part of Belgium where Cenozoic unconsolidated sandy and silty formations dominate which are especially vulnerable for erosion, and the southern part of Belgium and Luxembourg where Paleozoic and Mesozoic sandstones, carbonates, marls and shales are the prevalent lithologies. Here the shales are the most intensively eroded lithologies. This is especially reflected in the element patterns of Al2O3, MgO, K2O, Ga, Ni, Rb, Sc and V which negatively correlate with SiO2. Despite the human related pollution, the geological contrast between north and south Belgium is still recognisable in the geochemical pattern of the upper overbank and present-day stream sediment samples for the above-mentioned elements. Furthermore there is a clear increase in heavy metal contents (Zn, Cd, Pb, Cu), As and in certain locations in Be from the lower to the upper overbank sediment, as well as to the present-day stream sediment. The relative increase in element content allows to assess the degree of pollution and helps to define those drainage areas where more detailed research is needed. (C) 1998 Elsevier Science B.V. All rights reserved.